Phenanthridine derivatives



Patented Oct. 24, 1939 2,176,889

.- .,.UNITEDTATES PATENT OFFICE PHENANTHRIDINE DERIVATIVE S Walter G. Ghristiansen, Glen Ridge, N. J., and William Braker, Brooklyn, N.-Y., assignors to E. RSquibb & Sons, New York, N. Y., a corporation of New York No Drawing. Application December 22, 1934, Serial No. 758,824

2 Claims. 01. 260-288) This invention relates to, and has for its ob- 2.3 g. 3-nitro 9-methyl phenanthridine ject the provision of, certain phenanthridine derivatives and methods for the preparation thereof.

The compounds of this invention, which are 6 derived from phenanthridine i CH3 7 1 II v 1O prepared according to the method of Morgan and 4 Walls, 1932 J. C. S. 2225-2231, is added gradually, 15

with stirring, to a mixture of 15 cc. nitric acid (D 1.5) and 15 cc. concentrated sulfuric acid, the 2 mass during the addition and for fifty minutes thereafter being maintained at about 0; the mass is then poured into 200 cc. cold water; the Y resulting suspension is made ammoniacal and filtered; the residue is washed with water, dried in vacuo, and purified by suspending it in warm 1 acetone (to remove tarry contaminants), filter- 25 ing, washing with acetone, and drying in vacuo; I] fl and the desired compound is thus obtained in the N form of yellow crystals melting at 231-232".

3,7-diamino Q-methyl phenanthridine NHz.

wherein X represents a nitro, amino, or acylamino group; Y represents a nitro, amino, or acylamino group when X is an amino or 9. nitro group, but Y otherwise represents a nitro, amino, 'CH: or acylamino group or hydrogen; Z represents a halogen; R represents an alkyl; n represents 0 or 1; and R. represents an alkyl, a mononuclear 40 aryl, or a para-dialkylaminophenyl iminomethyl roup- 4o EXAMPLES 6.0 g. 3,7-dinitro 9-methyl phenanthridine is sus- 3, -dntr Q-meth l he anthrzdt 7 2 Z o y p n M pended in 100 cc. 4% hydrochloric acid; the mass N 2 is heated and stirred; 14 g. iron filings is added 45 during half an hour; the mixture is heated and stirred two hours and filtered; the residue is washed with Water, dried in vacuo, and extracted with chloroform in a Soxhlet apparatus; and on 5o evaporating the extract to a small volume and diluting it with petroleum ether, the desired compound is obtained in the form of yellowish-brown I crystals, which when filtered off, washed with NO petroleum ether, and dried in vacuo, melt at 205-207. 55

3,7-diacet'amzno-B-methyl phenanthridine NHCOCH:

OHaCONH CHaCONH 2 2.5 g. 3,7-diacetamino S-methyl phenanthridine is dissolved in 35 cc. hot nitrobenzene; 1.5 g. 111-- methyl sulfate is added; and upon cooling, the desired compound crystallizes from the solution in the form of reddish-brown needles, which, on being filtered 01f, washed with benzene, and dried in vacuo, are found to be very hygroscopic.

3,7-diamino 9,10-dz'methyl phenanthridinium chloride 2.5 g. 3,7-diacetamino 9,10-dimethyl phenanthri dine sulfate is refluxed four hours with 50 cc. 1:1 hydrochloric acid; there is added 50 cc. water and just enough aqueous ammonia to make the acidity of the solution only faint; and the desired compound separates out in the form of reddishbrown crystals.

3-amino 9-[(p -dimethylaminophenyl) immomethy IO-methyl phenanthridim'um chloride 2.6 g. 3-amino 9,10-dimethyl phenanthridinium chloride is dissolved in a mixture of cc. alcohol and 15 cc. water; 1.6 g. p-dimethylamino nitr0sobenzene in 2000. alcohol and three drops of piperidine are then added; the solution is refluxed one and one-half hours on the steam bath; 50 cc. water is added; the black crystalline substance separated out is filtered out; and on concentrating the filtrate to a small volume, the desired compound is obtained in the form of reddish-black crystals, Which on being filtered oiT, Washed with cold Water, and dried in vacuo, yield a powder melting at 119121.

Compounds of this invention are useful as antiseptic agents.

It is to be understood that the foregoing examples are merely illustrative and by no means limitative of the invention, which may be variously otherwise embodiedas with respect to the particular substituents at the 3, 7, 9, and 10 positions and the reactants and processes employedwithin the scope of the appended claims.

We claim:

1. 3,7 -diamino 9,10-dimethyl phenanthridinium chloride.

2. 3,7-diamino 9-a1kyl 10-alkyl phenanthridinium halides.

WALTER G. CI-IRISTIANSEN. WILLIAM BRAKER. 

